CN115591575B - Denitration catalyst and preparation method and application thereof - Google Patents
Denitration catalyst and preparation method and application thereof Download PDFInfo
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- CN115591575B CN115591575B CN202211355751.6A CN202211355751A CN115591575B CN 115591575 B CN115591575 B CN 115591575B CN 202211355751 A CN202211355751 A CN 202211355751A CN 115591575 B CN115591575 B CN 115591575B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 60
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000002002 slurry Substances 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 40
- 229910052802 copper Inorganic materials 0.000 claims abstract description 39
- -1 copper modified molecular sieve Chemical class 0.000 claims abstract description 37
- 239000011248 coating agent Substances 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 29
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 150000001879 copper Chemical class 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 31
- 239000000919 ceramic Substances 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 12
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims description 11
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims description 11
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims description 11
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 5
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 4
- 239000011707 mineral Substances 0.000 abstract description 4
- 239000002689 soil Substances 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 16
- 239000003546 flue gas Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052878 cordierite Inorganic materials 0.000 description 7
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a denitration catalyst, and a preparation method and application thereof. The preparation method of the denitration catalyst provided by the invention comprises the following steps: a) Mixing and heating copper salt, water and molecular sieve to obtain copper modified molecular sieve solution; b) Mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and then adjusting the pH value to obtain slurry; the structure auxiliary agent is at least one of oxide and mineral soil; c) And coating the slurry on the surface of a carrier, and then drying and roasting to obtain the denitration catalyst. The denitration catalyst prepared by the preparation method provided by the invention can widen the active temperature window and improve the NO x removal rate.
Description
Technical Field
The invention relates to the field of nitrogen oxide waste gas treatment, in particular to a denitration catalyst and a preparation method and application thereof.
Background
Nitrogen oxides (NO x) are one of the main atmospheric pollutants, which as primary pollutants itself can be harmful to human health, can irritate eyes, nose, throat and lungs of people, and are prone to respiratory diseases. More serious, NO x also can react with PM2.5 to form various secondary pollution, thereby causing various environmental problems such as acid rain, photochemical pollution and the like. Fossil fuel (coal, petroleum and natural gas) combustion is one of the main ways of generating NO x, especially the nitrogen oxides discharged by coal-fired boilers, and the control and treatment of the pollution of the nitrogen oxides are always research hot spots in the international environmental protection field.
The methods for controlling the emission of NO x in the prior art mainly comprise two main types, namely a low-nitrogen combustion technology, namely the generation of NO x is controlled in the fuel combustion process; and secondly, flue gas denitration technology, namely purifying generated waste gas containing NO x. In practical applications, the denitration efficiency of low-nitrogen combustion technology is generally lower than 60%, and the denitration efficiency cannot meet the increasingly strict emission standard. Therefore, effective flue gas denitration techniques are generally used.
Common flue gas denitration methods include a selective catalytic reduction method, a non-selective catalytic reduction method, an adsorption method, a catalytic decomposition method and the like, wherein the selective catalytic reduction method (SCR) is the most widely used method. Compared with other technologies, the Selective Catalytic Reduction (SCR) method uses ammonia, urea or ammonia water and the like as reducing agents, selectively reduces NO x in waste gas through a catalyst, converts the NO x into pollution-free N 2 and H 2 O, has the characteristics of low cost and high efficiency, and is the most widely applied denitration technology at present. The SCR technology has very remarkable control effect, small occupied area, easy operation and mature technology.
At present, catalysts in SCR denitration technology are divided into two types, namely high temperature and low temperature, wherein high temperature denitration (flue gas temperature is more than 300 ℃) is widely applied by a V-W/TiO 2 catalyst, and various components are added on the basis of the catalyst to improve the catalyst. The low-temperature denitration technology (the flue gas temperature is less than 300 ℃) can effectively avoid erosion of dust and alkali metal to the catalyst, and the service life of the catalyst is prolonged, so that the catalyst is more and more concerned by people. Wherein Mn or Mo contained low-temperature SCR denitration catalyst is most. However, the high-temperature or low-temperature denitration catalyst is difficult to reach the optimal working state under the unstable state of the temperature and the flow rate of the flue gas due to the narrow temperature window, and the low catalytic conversion efficiency and the poisoning deactivation phenomenon are displayed.
A large number of industrial combustion equipment including industrial boilers, small boilers and the like exist in China, and the temperature of flue gas discharged by coal is generally between 250 and 350 ℃ and lower than the temperature of flue gas of a coal-fired power station boiler (320 to 400 ℃), so that the denitration catalyst with a wide low-temperature window is developed, the technical requirements of flue gas denitration of the small industrial combustion equipment in China can be met, and the method has important significance and application prospect.
Disclosure of Invention
In view of the above, the present invention aims to provide a denitration catalyst, and a preparation method and application thereof. The denitration catalyst provided by the invention can widen the active temperature window and improve the NO x removal rate.
The invention provides a preparation method of a denitration catalyst, which comprises the following steps:
a) Mixing and heating copper salt, water and molecular sieve to obtain copper modified molecular sieve solution;
b) Mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and then adjusting the pH value to obtain slurry;
The structure auxiliary agent is at least one of oxide and mineral soil;
c) And coating the slurry on the surface of a carrier, and then drying and roasting to obtain the denitration catalyst.
Preferably, in the step a), the copper salt is at least one of copper nitrate, copper sulfate, copper oxalate, copper chloride and copper acetate;
the molecular sieve is at least one of SSZ-13, SAPO-34 and ZSM-5.
Preferably, in the step a), the mass ratio of copper to water to molecular sieve in the copper salt is (3-5) to 300 to (40-50);
the heating temperature is 60-80 ℃ and the heating time is 4-6 h.
Preferably, in the step b), the structural auxiliary agent is at least one of alumina powder, silica powder, diatomite, kaolin and montmorillonite;
the mass ratio of the structural auxiliary agent to the molecular sieve in the step a) is (50-60) to (40-50).
Preferably, in the step b), the binder is at least one of carboxymethyl cellulose, hydroxypropyl methyl cellulose, and polyacrylic resin;
the mass ratio of the binder to the molecular sieve in the step a) is (10-15) to (40-50).
Preferably, in step b), the pH is adjusted to a value of 5 to 6.
Preferably, in step c), the roasting temperature is 450-550 ℃ and the time is 1.5-2.5 h.
Preferably, in step c), the drying temperature is 110-130 ℃ and the drying time is 0.5-1.5 h;
the carrier is a honeycomb ceramic carrier;
the coating mode is dipping; the coating amount of the slurry on the carrier is 50-80 g/L.
The invention provides a denitration catalyst prepared by the preparation method in the technical scheme.
The invention also provides application of the denitration catalyst in selective catalytic reduction denitration.
According to the preparation method of the denitration catalyst, firstly, copper salt, water and a molecular sieve are mixed and heated to obtain a copper modified molecular sieve solution, wherein cations H + or Na + are generally distributed on the surface of the molecular sieve, and after the copper salt is added, cu 2+ is attached to the surface of the molecular sieve through ion exchange, so that the copper modified molecular sieve is formed; then, mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and adjusting the pH value to obtain mixed slurry; and then coating the slurry on the surface of the honeycomb ceramic carrier, drying and roasting, wherein the slurry is fully infiltrated on the surface of a pore canal of the honeycomb ceramic carrier, cu 2+ on the surface of the molecular sieve is oxidized into CuO after roasting, the binder is converted into an organic matter and reacts with oxygen to be dissipated, and finally the supported catalyst taking the honeycomb ceramic carrier as the carrier and carrying the CuO modified molecular sieve and the structure auxiliary agent is obtained, wherein the CuO modified molecular sieve and the structure auxiliary agent are in a certain bonding distribution state with the carrier, so that the obtained denitration catalyst can widen an active temperature window, improve the NO x removal rate, and has strong toxicity resistance and long service life. In addition, the conventional preparation process in the prior art generally comprises the steps of preparing an active component, drying and calcining, preparing the active component, an auxiliary agent and the like into slurry for coating, and finally drying and calcining; the invention adjusts the material formula, then carries out one-step pulping and coating, and then carries out drying and calcining, thereby saving the primary drying and calcining process and reducing the energy consumption.
Test results show that the denitration catalyst prepared by the invention has a wider active temperature window which can reach 150-450 ℃, and the NO removal rate reaches more than 79 percent under the temperature window; the denitration effect is further obviously improved when the temperature window is between 200 and 400 ℃, and the NO removal rate reaches more than 91 percent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a graph showing the effect of the catalytic denitration test in example 6.
Detailed Description
The invention provides a preparation method of a denitration catalyst, which comprises the following steps:
a) Mixing and heating copper salt, water and molecular sieve to obtain copper modified molecular sieve solution;
b) Mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and then adjusting the pH value to obtain slurry;
The structure auxiliary agent is at least one of oxide and mineral soil;
c) And coating the slurry on the surface of a carrier, and then drying and roasting to obtain the denitration catalyst.
Regarding step a):
a) And mixing and heating copper salt, water and molecular sieve to obtain copper modified molecular sieve solution.
In the present invention, the copper salt is preferably at least one of copper nitrate, copper sulfate, copper oxalate, copper chloride and copper acetate. The source of the copper salt is not particularly limited in the present invention, and the copper salt is commercially available.
In the present invention, the molecular sieve is preferably at least one of SSZ-13, SAPO-34 and ZSM-5. The source of the molecular sieve is not particularly limited, and the molecular sieve is commercially available.
In the invention, the mass ratio of copper to water to molecular sieve in the copper salt is preferably (3-5) to 300 to (40-50), and can be specifically 3:300:40, 3:300:45, 3:300:50, 4:300:40, 4:300:45, 4:300:50, 5:300:40, 5:300:45 and 5:300:50.
In the present invention, the temperature at which the above 3 materials are mixed and heated is preferably 60 to 80 ℃, specifically 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃. The heating time is preferably 4 to 6 hours, and specifically may be 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours.
In the present invention, stirring is preferably accompanied during the heating. The stirring speed is preferably 200-300 rpm, and can be 200rpm, 250rpm and 300rpm; the stirring time is preferably 4 to 6 hours, and specifically may be 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours.
In the present invention, step a) preferably comprises in particular: firstly, copper salt and water are stirred and mixed, molecular sieve is added and continuously stirred at the water bath temperature of 60-80 ℃, so that copper modified molecular sieve solution is obtained.
Regarding step b):
b) And mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and then adjusting the pH value to obtain slurry.
In the invention, the structural auxiliary agent is at least one of oxide and mineral soil, preferably at least one of alumina powder, silica powder, diatomite, kaolin and montmorillonite. Wherein the D90 particle diameter of the alumina powder is preferably 11-13 μm, and the D90 particle diameter of the silica powder is preferably 10-12 μm. In the invention, the mass ratio of the structural aid to the molecular sieve in the step a) is preferably (50-60) to (40-50), and can be specifically 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49 and 50:50.
In the present invention, the binder is preferably at least one of carboxymethyl cellulose, hydroxypropyl methyl cellulose, and polyacrylic resin. In the invention, the mass ratio of the binder to the molecular sieve in the step a) is preferably (10-15) to (40-50), and can be specifically 10:40, 11:43, 12:45, 13:45, 14:44 and 15:50.
In the present invention, the mode of mixing the above 3 materials is not particularly limited, and the materials may be uniformly mixed, such as stirring and mixing. After the above mixing, the pH value is adjusted. In the present invention, the pH is preferably adjusted to 5 to 6, and specifically may be 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9, 6.0. In the invention, the regulator used for regulating the pH value is an acid regulator; the acid regulator is preferably acid liquor; the acid liquid is preferably a strong acid, and can be hydrochloric acid, sulfuric acid or nitric acid. Through adjusting the pH value, the fluidity of the solution can be improved, the subsequent coating uniformity can be improved, the bonding effect of the carrier can be improved, and the product performance can be improved. After the above treatment, a slurry was obtained.
Regarding step c):
c) And coating the slurry on the surface of a carrier, and then drying and roasting to obtain the denitration catalyst.
In the present invention, the support is preferably a honeycomb ceramic support, more preferably a cordierite honeycomb ceramic support. In some embodiments of the invention, the honeycomb ceramic carrier has dimensions of 10cm by 5cm.
In the present invention, the coating means for coating the slurry on the support is preferably dipping. The temperature at which the slurry is used to impregnate the honeycomb ceramic carrier is not particularly limited, and the impregnation is carried out at normal temperature. The amount of the two materials used in the impregnation is not particularly limited, and the slurry can completely submerge the honeycomb ceramic carrier. And after the honeycomb ceramic carrier is fully immersed in the slurry, taking out the carrier, and removing redundant slurry residual liquid in the pore channels of the honeycomb ceramic carrier. In the invention, the mode of removing the redundant slurry residual liquid in the pore canal of the honeycomb ceramic carrier can be specifically to adopt high-pressure air blowing. In the present invention, the coating amount of the slurry on the carrier is preferably 50 to 80g/L, and may be specifically 50g/L, 60g/L, 70g/L, 80g/L. The slurry of the present invention is coated in a low amount sufficient to improve the catalytic effect at the above low coating amount.
In the present invention, the above-mentioned coating is followed by drying. In the present invention, the drying temperature is preferably 110 to 130 ℃, and specifically 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃. The drying time is preferably 0.5 to 1.5 hours, and may specifically be 0.5 hours, 1.0 hours, or 1.5 hours.
In the present invention, the above-mentioned drying is followed by calcination. In the present invention, the baking temperature is preferably 450 to 550 ℃, specifically 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃. The heat preservation time of the roasting is preferably 1.5-2.5 h, and can be specifically 1.5h, 2h and 2.5h. And (3) roasting to obtain the denitration catalyst.
The preparation method provided by the invention is a liquid-phase ion exchange method, firstly, copper salt, water and a molecular sieve are mixed and heated to obtain a copper modified molecular sieve solution, wherein cations H + or Na + are generally distributed on the surface of the molecular sieve, and after the copper salt is added, cu 2+ is attached to the surface of the molecular sieve through ion exchange, so that the copper modified molecular sieve is formed; then, mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and adjusting the pH value to obtain mixed slurry; then, coating the slurry on the surface of a honeycomb ceramic carrier, drying and roasting, fully infiltrating the slurry on the surface of a pore canal of the honeycomb ceramic carrier, oxidizing Cu 2+ on the surface of a molecular sieve into CuO after roasting, converting a binder into an organic matter, reacting with oxygen and dissipating, and finally obtaining the supported catalyst taking the honeycomb ceramic carrier as the carrier and carrying the CuO modified molecular sieve and the structure auxiliary agent, wherein the CuO modified molecular sieve and the structure auxiliary agent are in a certain combined distribution state with the carrier, so that the obtained denitration catalyst can widen an active temperature window, improve the NO x removal rate, and has strong toxicity resistance and long service life; moreover, the preparation method is simple and feasible.
The invention also provides a denitration catalyst prepared by the preparation method in the technical scheme. In the invention, the denitration catalyst comprises a carrier and an object carried on the carrier. The carried object comprises a CuO modified molecular sieve and a structure aid. In the denitration catalyst of the present invention, the mass ratio of the supported material to the carrier is preferably (50 to 80) to (260 to 270).
The invention also provides application of the denitration catalyst in Selective Catalytic Reduction (SCR) denitration.
The invention also provides a Selective Catalytic Reduction (SCR) process, wherein the catalyst is the denitration catalyst in the technical scheme. The process of the selective catalytic reduction process is not particularly limited, and is carried out according to a conventional method in the art, and only the catalyst thereof is replaced by the denitration catalyst of the present invention.
The denitration catalyst provided by the invention is prepared by the preparation method, firstly copper salt, water and a molecular sieve are mixed and heated to obtain a copper modified molecular sieve solution, wherein cations H + or Na + are generally distributed on the surface of the molecular sieve, and after the copper salt is added, cu 2+ is attached to the surface of the molecular sieve through ion exchange to form the copper modified molecular sieve; then, mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and adjusting the pH value to obtain mixed slurry; and then coating the slurry on the surface of the honeycomb ceramic carrier, drying and roasting, wherein the slurry is fully infiltrated on the surface of a pore canal of the honeycomb ceramic carrier, cu 2+ on the surface of the molecular sieve is oxidized into CuO after roasting, the binder is converted into an organic matter and reacts with oxygen to be dissipated, and finally the supported catalyst taking the honeycomb ceramic carrier as the carrier and carrying the CuO modified molecular sieve and the structure auxiliary agent is obtained, wherein the CuO modified molecular sieve and the structure auxiliary agent are in a certain bonding distribution state with the carrier, so that the obtained denitration catalyst can widen an active temperature window, improve the NO x removal rate, and has strong toxicity resistance and long service life. In addition, the conventional preparation process in the prior art generally comprises the steps of preparing an active component, drying and calcining, preparing the active component, an auxiliary agent and the like into slurry for coating, and finally drying and calcining; the invention adjusts the material formula, then carries out one-step pulping and coating, and then carries out drying and calcining, thereby saving the primary drying and calcining process and reducing the energy consumption.
Test results show that the denitration catalyst prepared by the invention has a wider active temperature window which can reach 150-450 ℃, and the NO removal rate reaches more than 79 percent under the temperature window; the denitration effect is further obviously improved when the temperature window is between 200 and 400 ℃, and the NO removal rate reaches more than 91 percent.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention. In the following examples, the raw materials used were commercial products unless otherwise specified. The raw material dimension specifications are consistent with those in the technical scheme.
Example 1
A) Adding water into copper nitrate, stirring (the speed is 200 rpm), stirring the copper nitrate in a water bath at the temperature of 60 ℃, adding molecular sieve SSZ-13, and continuously stirring for 6 hours to obtain copper modified molecular sieve solution;
Wherein the mass ratio of copper to water to molecular sieve in copper nitrate=3:300:40.
B) Adding aluminum oxide and carboxymethyl cellulose into the copper modified molecular sieve solution, mixing, and adding hydrochloric acid to adjust the pH value to 5 to obtain slurry;
wherein the mass ratio of alumina to molecular sieve in step a) is=60:40, and the mass ratio of carboxymethyl cellulose to molecular sieve in step a) is=10:40.
C) And (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Example 2
A) Adding water into copper acetate, stirring (the speed is 300 rpm), stirring the copper acetate in a water bath at the temperature of 80 ℃, adding molecular sieve ZSM-5, and continuously stirring for 4 hours to obtain copper modified molecular sieve solution;
wherein the mass ratio of copper to water to molecular sieve in copper acetate=5:300:50.
B) Adding montmorillonite and polyacrylic resin into the copper modified molecular sieve solution, mixing, and adding sulfuric acid to adjust the pH value to 6 to obtain slurry;
Wherein, the mass ratio of montmorillonite to the molecular sieve in the step a) is=50:50, and the mass ratio of polyacrylic resin to the molecular sieve in the step a) is=15:50.
C) And (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Example 3
A) Adding water into copper sulfate, stirring (the speed is 250 rpm), stirring the water bath at the temperature of 70 ℃, adding molecular sieve SAPO-34, and continuously stirring for 5 hours to obtain copper modified molecular sieve solution;
Wherein the mass ratio of copper to water to molecular sieve in copper sulfate=4:300:45.
B) Adding diatomite and hydroxypropyl methylcellulose into the copper modified molecular sieve solution, mixing, and adding nitric acid to adjust the pH value to 5.5 to obtain slurry;
Wherein, the mass ratio of diatomite to the molecular sieve in the step a) is=55:45, and the mass ratio of hydroxypropyl methylcellulose to the molecular sieve in the step a) is=12:45.
C) And (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Example 4
A) Adding water into copper chloride, stirring (the speed is 250 rpm), stirring the copper chloride in a water bath at the temperature of 70 ℃, adding molecular sieve SAPO-34, and continuously stirring for 5 hours to obtain copper modified molecular sieve solution;
Wherein the mass ratio of copper to water to molecular sieve in copper chloride=4:300:45.
B) Adding kaolin and hydroxypropyl methylcellulose into the copper modified molecular sieve solution, mixing, and adding nitric acid to adjust the pH value to 5.5 to obtain slurry;
Wherein the mass ratio of kaolin to the molecular sieve in step a) is=55:45, and the mass ratio of hydroxypropyl methylcellulose to the molecular sieve in step a) is=13:45.
C) And (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Example 5
A) Adding water into copper oxalate, stirring (the speed is 250 rpm), stirring the water bath temperature is 70 ℃, adding molecular sieve SAPO-34, and continuously stirring for 5 hours to obtain copper modified molecular sieve solution;
Wherein the mass ratio of copper to water to molecular sieve in the copper oxalate=4:300:45.
B) Adding silicon oxide powder and hydroxypropyl methylcellulose into the copper modified molecular sieve solution, mixing, and adding nitric acid to adjust the pH value to 5.5 to obtain slurry;
Wherein, the mass ratio of silica powder to the molecular sieve in the step a) is=55:45, and the mass ratio of hydroxypropyl methylcellulose to the molecular sieve in the step a) is=14:45.
C) And (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Comparative example 1
The procedure is as in example 3, except that no kieselguhr construction aid is added in step b).
Comparative example 2
The same raw materials as in example 3 were used, except that the preparation was not carried out by a liquid phase ion exchange method, but by a solid phase reaction method, specifically as follows:
mixing CuO powder, molecular sieve SAPO-34, diatomite, hydroxypropyl methylcellulose and water, adding nitric acid after uniformly mixing, and adjusting the pH value to 5.5 to obtain slurry; and (3) coating the slurry on the surface of a cordierite honeycomb ceramic carrier with the coating amount of 50g/L, drying at 120 ℃ for 1h, and roasting at 500 ℃ for 2h to obtain the denitration catalyst.
Wherein, cu, molecular sieve SAPO-34, diatomite, hydroxypropyl methylcellulose and water are used in the CuO powder in the same ratio as in example 3.
Comparative example 3
The procedure is as in example 3, except that in step b) the pH is adjusted to 2.
Comparative example 4
The procedure is as in example 3, except that in step b), the pH is adjusted to 8.
Comparative example 5
The procedure is as in example 3, except that in step a) the molecular sieve is replaced by a KZ-1 molecular sieve.
Comparative example 6
The procedure is as in example 3, except that in step b) the diatomaceous earth construction aid is replaced by silicon carbide powder (D90 particle size 11 μm).
Example 6: product testing
The denitration catalysts obtained in examples 1 to 5 and comparative examples 1 to 6 were subjected to selective catalytic reduction, and the denitration rate of the denitration catalysts to low-temperature flue gas was tested, and the evaluation method was as follows:
The denitration activity experiment of the catalyst is carried out on a self-made catalyst test platform, and simulated flue gas is prepared according to the following proportion: the ammonia nitrogen ratio molar ratio is 1:1,O 2, the concentration is 6% (V/V), GHSV (gas space velocity per hour) =5000 h -1. By adopting the simulated flue gas, NO conversion rates at different temperature points are respectively measured on a self-made catalyst test platform. When the temperature of the reactor is stabilized to a certain temperature point, the simulated flue gas is introduced, after the reaction is carried out for 10min, the concentration of NO in the gas before and after the reaction is measured by using a flue gas analyzer, the continuous measurement time of each temperature point is 15min, the average value is taken, and the conversion rate of NO, namely the denitration rate, is calculated according to the following formula:
Conversion of no= [ (NO in-NOout)/NOin ] ×100%
Wherein, NO in is the concentration of NO in the simulated flue gas before entering the reactor, and NO out is the concentration of NO in the flue gas after denitration and purification of the reactor. The test results of the denitration rate are shown in fig. 1, and fig. 1 is a graph showing the catalytic denitration test effect in example 6. The denitration rates at the individual temperature points in examples 1 to 5 in FIG. 1 are summarized in Table 1, and the denitration rates at the different temperature points in comparative examples 1 to 2 are also shown in Table 1.
Table 1: denitration rate at different temperature points
As can be seen from the test results of FIG. 1 and Table 1, the catalysts obtained in examples 1-5 of the present invention have a wide active temperature window, which can reach 150-450 ℃, and the NO removal rate reaches over 79% in the temperature window; the denitration effect is further obviously improved when the temperature window is between 200 and 400 ℃, and the NO removal rate reaches more than 91 percent. Compared with the example 3, the catalyst obtained in the comparative example 1 has obviously narrowed active temperature window and reduced denitration rate, and the addition of the structural auxiliary agent and other components in the invention proves that the catalyst can effectively stabilize copper and molecular sieve, can effectively widen the active temperature window and improve the denitration rate. Compared with the example 3, the catalyst obtained in the comparative example 2 has obviously narrowed active temperature window and reduced denitration rate, and the invention proves that the catalyst prepared by the liquid phase ion exchange method can enable copper ions to go deep into a molecular sieve framework structure to play a synergistic effect, and can effectively widen the active temperature window and improve the denitration rate. Compared with the example 3, the catalyst obtained in the comparative examples 3-4 has obviously narrowed activity temperature window and reduced denitration rate, and the invention is beneficial to improving the quality of slurry and further improving the catalytic performance of the product by controlling the pH value in the step b) to be too low or too high. Compared with the example 3, the catalyst obtained in the comparative example 5 has obviously narrowed activity temperature window and reduced denitration rate, and the invention proves that the catalyst is favorable for improving the catalytic performance of the catalyst by utilizing certain matching property between copper salt and molecular sieve and modifying certain molecular sieve. Compared with the example 3, the catalyst obtained in the comparative example 6 has obviously narrowed activity temperature window and reduced denitration rate, and the invention proves that the catalyst can be better matched with other components by adopting a certain substance as a structural auxiliary agent, thereby being beneficial to improving the catalytic performance of the catalyst.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (9)
1. The preparation method of the denitration catalyst is characterized by comprising the following steps of:
a) Mixing and heating copper salt, water and molecular sieve to obtain copper modified molecular sieve solution;
The molecular sieve is at least one of SSZ-13, SAPO-34 and ZSM-5;
b) Mixing the copper modified molecular sieve solution with a structure auxiliary agent and a binder, and then regulating the pH value to 5-6 to obtain slurry;
The structural auxiliary agent is at least one of alumina powder, silica powder, diatomite, kaolin and montmorillonite;
c) And coating the slurry on the surface of a carrier, and then drying and roasting to obtain the denitration catalyst.
2. The method according to claim 1, wherein in step a), the copper salt is at least one of copper nitrate, copper sulfate, copper oxalate, copper chloride and copper acetate.
3. The preparation method according to claim 1, wherein in the step a), the mass ratio of copper to water to molecular sieve in the copper salt is (3-5) to 300 to (40-50);
the heating temperature is 60-80 ℃ and the heating time is 4-6 h.
4. The preparation method according to claim 1, wherein the mass ratio of the structure aid to the molecular sieve in the step a) is (50-60) to (40-50).
5. The method of claim 1, wherein in step b), the binder is at least one of carboxymethyl cellulose, hydroxypropyl methylcellulose, and polyacrylic resin;
the mass ratio of the binder to the molecular sieve in the step a) is (10-15) to (40-50).
6. The method according to claim 1, wherein in step c), the calcination temperature is 450 to 550 ℃ for 1.5 to 2.5 hours.
7. The method according to claim 1, wherein in step c), the drying temperature is 110 to 130 ℃ for 0.5 to 1.5 hours;
the carrier is a honeycomb ceramic carrier;
the coating mode is dipping; the coating amount of the slurry on the carrier is 50-80 g/L.
8. A denitration catalyst produced by the production method as claimed in any one of claims 1 to 7.
9. Use of the denitration catalyst as claimed in claim 8 in selective catalytic reduction denitration.
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